Temperature-Stable Oxynitride Phosphor and Light Source Comprising a Corresponding Phosphor Material

ABSTRACT

A thermally stable phosphor made of the M-Si—O—N system, having a cation M and an activator D, M being represented by Ba or Sr alone or as a mixture and optionally also being combined with at least one other element from the group Ca, Mg, Zn, Cu. The phosphor is activated with Eu or Ce or Tb alone or as a mixture, optionally in codoping with Mn or Yb. The activator D partially replaces the cation M. The phosphor is produced from the charge stoichiometry MO—SiO 2 —SiN 4/3  with an increased oxygen content relative to the known phosphor MSi 2 O 2 N 2 :D, where MO is an oxidic compound.

TECHNICAL FIELD

The invention relates to a thermally stable phosphor, preferably for use in light sources, according to the precharacterizing clause of claim 1. The invention also concerns a high-efficiency phosphor of the SiON class according to the precharacterizing clause of claim 1. The invention also concerns a light source produced therewith and to a method for producing such a phosphor.

PRIOR ART

EP-A 1 413 618 discloses a phosphor which belongs to the oxynitride class and has the composition MSi₂O₂N₂:Z. M is primarily Ca, Ba or Sr, and the activator Z is primarily Eu. They are referred to here as SiONs. This phosphor can be excited well in the UV and blue spectral ranges. It is suitable for light sources such as LEDs.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide a narrowband thermally stable phosphor, which preferably emits in the green range. The phosphor is intended to be particularly suitable for use with UV and blue LEDs. Other applications, however, are not excluded.

This object is achieved by the characterizing features of claim 1.

Particularly advantageous configurations may be found in the dependent claims.

The systems known to date are distinguished in the case of nitrides by very high efficiency and thermal stability. However, no efficient narrowband-emitting systems with a peak wavelength at 525-535 nm are as yet known. Although green orthosilicates and thiogallates emit with a narrow band and are also very efficient at room temperature, they nevertheless have a very poor temperature response. This means that their luminescent efficiency LE decreases very strongly with an increasing temperature (typically, <10% at 225° C.). However, the thermal stability of the luminescence is worse than in the case of nitrides. Furthermore, shorter-wavelength emission is desirable in certain applications, particularly in order to achieve a higher useful visual effect.

For many applications, for example in LCD backlights or for RPTV (rear projection television), very thermally stable phosphors which can be excited in the blue or near UV ranges, with a peak wavelength of between 525 and 535 nm, are required. This wavelength ideally matches the conventional color filters and allows good color rendering. The good thermal stability is necessary since the phosphor can be heated greatly owing to the high chip temperatures at high powers and owing to the heat evolved in the phosphor particle, with high radiation fluxes. This can result in temperatures of up to 200° C.

The cause of the second heating mechanism is the so-called Stokes shift, i.e. the energy difference between absorbed and emitted photons, which is converted into heat in the phosphor.

To date, there is not any known narrowband green phosphor which even at elevated temperatures, preferably at least 125° C., in particular at least 175° C., still has high efficiencies, specifically at least 80%, in particular even at least 90% of the efficiency at room temperature. The term narrow band is intended to mean an FWHM of at most 70 nm. The term green phosphor is intended to mean a phosphor whose peak wavelength lies in the range of from 520 to 540 nm, particularly in a range of from 525 to 535 nm.

An entirely novel phosphor has been discovered in the phase system BaO—SiO₂—Si₃N₄. This phosphor differs from the known BaSi₂O₂N₂ by a substantially higher oxygen content, and from the known silicates such as Ba₂SiO₄, BaSi₂O₅ and BaSiO₃ by a significant nitrogen component in the host lattice. The new phase has an XRD reflection pattern which differs from all known silicates and SiONs. It implies a high symmetry of the new compound. The charge stoichiometry can preferably be described in an exemplary embodiment by Ba₉Si₂₁O₃₆N₁₀.

The activator D, which replaces Ba, is preferably either Eu alone or together with Yb. The Yb component should not however be more than 10 mol % of D, preferably a component in the range of from 1 to 5%.

The novel phosphor has a much better thermal stability than known green phosphors such as (Sr,Ba)₂SiO₄:Eu (orthosilicate) or SrGa₂(S,Se)₄:Eu (thiogallate type). While the best orthosilicates available on the market still have about 25-30% of their room temperature efficiency at 175° C., the new compound here has 80-90% and therefore represents a technical breakthrough.

The novel phosphor shows very good thermal and chemical stability. It can be used very well for example for white LEDs, color-on-demand (COD), RPTV/TV backlighting LEDs and electric lamps such as fluorescent lamps.

A production method for the novel phosphor is furthermore provided.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention will be explained in more detail below with the aid of an exemplary embodiment. In the figures:

FIG. 1 shows the stability of the efficiency of a novel phosphor in relation to thermal quenching;

FIG. 2 shows the XRD reflections of a novel phosphor;

FIG. 3 shows an overview of the phase diagram of the system of the educts BaCO₃—SiN_(4/3)—SiO₂ with 2% Eu for Ba;

FIG. 4 shows the emission spectra with the charge stoichiometry Ba_(2-x)Eu_(x)Si₅O₉N₂ for various Eu concentrations;

FIG. 5 shows emission spectra with the charge stoichiometry Ba_(2-x-y)Sr_(y)Eu_(x)Si_(4.6)O_(9.2)N_(1.8);

FIG. 6 shows the emission spectra with various charge stoichiometries;

FIG. 7 shows the powder brightness as a function of the activator concentration with 400 nm excitation;

FIG. 8 shows the powder brightness as a function of the activator concentration with 460 nm excitation;

FIG. 9 shows the excitability of the new Ba—SiONs with different Eu concentrations;

FIG. 10 shows the excitability of the new Ba—SiONs for various charge mixtures;

FIG. 11 shows the basic structure of a light source for green light;

FIG. 12 shows the basic structure of a light source for white light;

FIG. 13 shows the basic structure of a discharge lamp;

FIG. 14 shows the emission spectrum of a Tb³⁺-doped sample of the phosphor (Ba_(0.95)Tb_(0.05))₂Si₅O₉N₂;

FIG. 15 shows the emission spectrum of a Ce³⁺-doped sample of the phosphor (Ba_(0.98)Ce_(0.02))₂Si₅O₉N₂;

FIG. 16 shows the excitation spectrum of a Ce³⁺-doped sample of the phosphor (Ba_(0.98)Ce_(0.02))₂Si₅O₉N₂;

FIG. 17 shows a comparison of the powder brightness with pure Eu doping and codoping with Yb;

FIG. 18 shows a comparison of the powder brightness for various charge stoichiometries;

FIG. 19 shows a comparison of the powder brightness as a function of the holding time;

FIG. 20 shows the powder brightness as a function of the fluxing agent additive;

FIG. 21 shows an overview of the phase diagram of the system of the educts BaCO₃—SiN_(4/3)—SiO₂ with 2% Eu for Ba with the preparation of particularly suitable phosphors.

PREFERRED EMBODIMENT OF THE INVENTION

FIG. 1 shows the stability of the efficiency in relation to thermal quenching. The newly discovered phosphor phase has an outstanding thermal efficiency of its emission compared with all other known, usually Eu²⁺-activated systems emitting with a narrow band at about 525 to 535 nm. FIG. 1 shows a comparison between the Ba—SiON phase according to the invention and an SrBa orthosilicate with similar emission, which represents the best prior art.

A specific novel phosphor is BaSi_(2.3)O_(4.3)N_(0.9):Eu(2%)=Ba₂Si_(4.6)O_(8.6)N_(1.8):Eu(2%). Its production will be described in more detail below.

The starting substances 11.784 g BaCO₃, 6.102 g SiO₂, 1.900 g Si₃N_(4/3) and 0.214 g Eu₂O₃, optionally with the addition of conventional fluxing agents, are homogenized for several hours, in particular for from 2 to 8 hours.

The charge mixture is annealed in Al₂O₃ crucibles with a lid under reducing conditions, preferably forming gas, at about 1200 to 1400° C. for several hours, in particular from 3 to 10 hours. The term reducing conditions is intended to mean the use of an inert gas, preferably N₂ with the addition of H₂. The H₂ component in the forming gas should be from 0 to 20% (including the endpoint values); for example, 4% H₂ are used.

The anneal cake is ground in the conventional way, and the phosphor powder is then optionally subjected to a second anneal at from 850 to 1450° C. under reducing conditions (forming gas). The H₂ component in the forming gas should be from 0 to 20% (including the endpoint values); for example, 4% H₂ are used.

In a second exemplary embodiment, the production method is similar but the following weigh-in of the starting substances is selected for the target stoichiometry Ba₂Si₅O₉N₂:

11.473 g BaCO₃, 6.238 g SiO₂, 2.081 g Si₃N₄ and 0.209 g Eu₂O₃.

In a third exemplary embodiment, the production method is similar but the following weigh-in of the starting substances is selected for a preferred target stoichiometry Ba₉Si₂₁O₃₆N₁₀: 11.864 g BaCO₃, 5.529 g SiO₂, 2.391 g Si₃N₄ and 0.216 g Eu₂O₃.

It is advantageous to use typical fluxing agents such as fluorides, chlorides and oxides (see Tab. 1). Specific exemplary embodiments are BaF₂ or BaCl₂, as well as other compounds studied in Tab. 1

The charge stoichiometry is not identical to the product stoichiometry, but serves as a rough guide. For example, according to elementary analysis, the charge stoichiometry BaSi_(2.3)O_(4.3)N_(0.9) leads to a phosphor with the approximate product stoichiometry Ba₂Si₅O₉N₂. The indices of the product stoichiometries as indicated here are in general typically accurate to 10%, if the index for Ba is taken as a fixed point.

TABLE 1 Fluxing agent Rel. bright- Sample BPxx/07 (additive) Rel. QE ness 230 None 100% 100% 311 2 mol % H₃BO₃ 102% 122% 312 2 mol % NH₄Cl 102% 119% 313 2 mol % BaF₂ 111% 131% 314 2 mol % La₂0₃ 102% 119%

FIG. 2 shows the XRD reflections of the novel phosphor. The XRD reflections of the new phase can be described best with a trigonal or hexagonal space group with a=7.5094(1) Å and c=6.4753(1) Å with a cell volume V=316.23 Å³. The space groups P3 or P-3 give an unequivocal description of the barium positions taking into account the volume increments of possible composition.

Tab. 2 shows the reflections with the position of the reflections with lattice plane spacings d_(hk1) and estimated peak intensities. The errors in the lattice spacings may be up to +−2%.

TABLE 2 Reflection Positions and Intensities Reflection No. d_(hkl) (Å) Intensity 1 6.49 Medium 2 4.59 Medium 3 3.75 Strong 4 3.25 Strong 5 2.90 Strong 6 2.45 Medium 7 2.30 Medium 8 2.16 Medium 9 2.05 Medium 10 1.96 Medium 11 1.87 Weak 12 1.80 Medium 13 1.62 Medium 14 1.58 Weak 15 1.45 Weak 16 1.42 Weak 17 1.38 Weak 18 1.35 Weak 19 1.30 Weak 20 1.27 Weak 21 1.25 Weak 22 1.23 Weak 23 1.21 Weak

FIG. 3 shows an overview of the phase diagram of the system of the educts BaCO₃—SiN_(4/3)—SiO₂ with 2% Eu for Ba.

The two most important already known phosphor phases in the system are:

-   -   the blue-green BaSi₂O₂N₂:Eu and the blue-green Ba₂SiO₄:Eu. These         two are denoted by arrows. Both systems show a much worse         temperature response than the phosphor according to the         invention. The circle denotes the particularly high-efficiency         region of the new phase. Virtually or entirely pure-phase novel         phosphors are denoted by a black circle, mixed phases with other         phases by a shaded circle and other phases alone by a white         circle. Depending on the charge stoichiometry, the other phases         are Si₃N₄, Ba orthosilicate, SiO₂, Ba₂Si₅N₈, BaSiO₃, BaSi₂O₅,         BaO, Ba₃SiO₅ and Ba₂Si₃O₈. Good results for the novel phase are         provided by a charge stoichiometry which lies approximately in a         square with the following corners:

(1) SiO₂:SiN_(4/3):BaCO₃=0.525:0.25:0.225

(corresponding to Ba_(1.8)Si_(6.2)O_(10.2)N_(2.67));

(2) SiO₂:SiN_(4/3):BaCO₃=0.425:0.25:0.325

(corresponding to Ba_(2.6)Si_(5.4)O_(9.4)N_(2.67));

(3) SiO₂:SiN_(4/3):BaCO₃=0.475:0.15:0.375

(corresponding to Ba₃Si₅O_(10.62)N_(1.6));

(4) SiO₂:SiN_(4/3):BaCO₃=0.575:0.15:0.275

(corresponding to Ba_(2.2)Si_(5.8)O_(11.4)N_(1.6)).

The novel phase composition exhibits a particularly pure phase when the BaCO₃:SiO₂ ratio in the charge mixture is between 1:1.5 and 1:2. SiN_(4/3) is then added thereto. Overall, the SiN_(4/3) component should be at least 15%, and at most 55%. The best samples are obtained with 20-30% SiN_(4/3).

Tab. 3 shows screening of the phase space, the phosphor efficiencies, the color loci and the dominant emission wavelength for 400 nm excitation with a 2% Eu activator concentration (substitution of Ba site) being specified.

With 2% Eu doping, the new phase typically emits at about λdom=537±3 nm. All other known pure Eu-doped Ba silicates and Ba—SiONs emit at much shorter wavelengths. In this regard reference is made to sample BP128/07, which comprises only Ba silicate as a phosphor compound. The phosphor BaSi₂O₂N₂:Eu (about 500 nm) is not in fact formed at all with the selected synthesis conditions—in particular with this low temperature.

Tabs 4a/4b show the efficiencies of selected charge stoichiometries (high phase purity) for various Eu concentrations, and specifically for excitation wavelengths of 400 and 460 nm respectively.

A second anneal (samples with index ‘a’) generally improves the crystallinity and thus increases the efficiency of the samples. For 460 nm excitation, somewhat higher Eu concentrations are generally advantageous. This corresponds to what is found when studying the excitation spectra.

FIG. 4 shows the emission spectra with the charge stoichiometry Ba_(2-x)Eu_(x)Si₅O₉N₂ for various Eu concentrations in the range of from x=0.02 to x=0.2. They correspond to 1, 5 and 10 mol % of M. Higher Eu concentrations are nevertheless readily possible.

FIG. 5 shows emission spectra with the charge stoichiometry Ba_(2-x-y)Sr_(y)Eu_(x)Si_(4.6)O_(9.2)N_(1.8) for fixed x=0.04 (2% Eu) with y=0 and y=0.48 (about 25% Sr for Ba). As expected, and the incorporation of a smaller ions such as Sr leads to longer-wavelength emission. A smaller ion leads to a stronger interaction with the surrounding lattice atoms, and this in turn leads to a long-wavelength shift. Specifically, the emission is shifted here by about 20 nm from 523 nm to 543 nm, i.e. the novel phosphor can readily be adapted to corresponding applications.

FIG. 6 shows the emission wavelength with three different charge stoichiometries. With charge stoichiometries close to the phase determined by chemical analysis, roughly Ba₂Si₅O₉N₂, a very similar dominant emission wavelength of the Eu-doped phosphor is respectively found.

FIG. 7 shows the relative powder brightness as a function of the activator concentration with an excitation wavelength of 400 nm. The preferred Eu concentration lies between 5 and 15% Eu.

FIG. 8 shows the relative powder brightness as a function of the activator concentration with the excitation wavelength 460 nm. The preferred Eu concentration lies between 5 and 15 mol % Eu. This powder brightness is a measure of the ratio between the number of radiated photons and the number of incident photons.

FIG. 9 shows the excitability of the new Ba—SiON (here, charge stoichiometry Ba_(2-x)Eu_(x)Si_(4.6)O_(9.2)N_(1.8)) with different Eu concentrations. The phosphor can be excited well in a wide spectral range of about 250 to 470 nm.

FIG. 10 shows the excitability of the new Ba—SiON (here: three different charge mixtures). Relatively independently of the exact charge stoichiometry, a similar excitation spectrum is respectively obtained for the specified charge stoichiometries. With the sample Ba₃Si₆O₁₂N₂, which has a 2% Eu component, a minor heterogeneous phase component leads to a slight deformation of the spectrum.

The phosphors according to the invention can also be used in connection with other UV or blue light sources such as molecular radiators (for example In discharge lamps), or blue OLEDs or in combination with blue EL phosphors.

They make it possible to produce efficient color-stable LEDs or LED modules based on a conversion LED. Other fields of application are LEDs with good color rendering, color-on-demand LEDs or white OLEDs. The new phosphor can also be used in conventional lamps, but also for electrical devices such as CRTs, PDPs, FEDs etc.

The basic structure of a light source for green light is explicitly shown in FIG. 11. The light source is a semiconductor component having a chip 1 of the InGaN type with a peak emission wavelength in the UV range, for example 405 nm, which is embedded in an opaque base package 8 in the region of a recess 9. The chip 1 is connected via a bonding wire 4 to a first terminal 3, and directly to a second electrical terminal 2. The recess 9 is filled with an encapsulation compound 5, which contains as main constituents a silicone resin (80 to 90 wt %) and phosphor pigments 6 (typically less than 20 wt %). The recess has a wall 7, which acts as a reflector for the primary and secondary radiation of the chip 1, or the pigments 6. The primary radiation of the UV LED is fully converted into green light by the phosphor. The phosphors used is the Ba—SiON Ba₂Si₅O₉N₂:Eu described above.

A light source for white light can be produced in a similar way by using three phosphors, which are excited by the UV radiation source, to emit red, green and blue light. The green phosphor is the novel Ba—SiON Ba₂Si₅O₉N₂:Eu, the red phosphor is for example Ca₅Al₄Si₈N₁₈:Eu or a nitridosilicate (Ca,Sr)₂Si₅N₈:Eu and the blue phosphor is for example an aluminate or phosphate phosphor, such as BAM:Eu or SCAP:Eu or the like.

The structure of another light source for white light is explicitly shown in FIG. 12. The light source is a semiconductor component 16 of the LED type having a blue-emitting chip 11 of the InGaN type with a peak emission wavelength of for example 460 nm. The semiconductor component 16 is embedded in an opaque base package 18 with a side wall 15 and a lid 19. The chip is the primary light source for two phosphors. The first phosphor 14 is the oxynitridosilicate Ba₂Si₅O₉N₂:Eu(10%), which partially converts the primary radiation of the chip 13 and transforms it into green radiation with a peak emission of 530 nm. The second phosphor is the novel nitridosilicate (Ca,Sr,Mg)₅Al₄Si₈N₁₈:Eu, which partially converts the primary radiation of the chip 13 and transforms it into red radiation with a peak emission of 630-660 nm.

A particular advantage of using a long-wavelength primary light source (450 to 465 nm) for the luminescence conversion LED is that it avoids problems with ageing and degradation of the package and resin or phosphor, so that a long lifetime is achieved.

In another exemplary embodiment, a UV LED (about 380 nm) is used as a primary light source for a white RGB luminescence conversion LED, in which case problems with ageing and degradation of the package and resin or phosphor must be avoided as much as possible by additional measures known per se, such as careful selection of the package material, adding UV-resistant resin components. The great advantage of this solution is the low viewing angle dependency of the emission, and the high color stability.

FIG. 13 shows a low-pressure discharge lamp 20 with a mercury-free gas fill 21 (schematized) which contains an indium compound and a buffer gas similarly as in WO 02/10374, wherein a layer 22 of Ba—SiON is present. In general, so-called triple-band phosphors are used in fluorescent lamps. To this end, a blue phosphor and a red phosphor are added. BAM:Eu or BaMgAl₁₀O₁₇:Eu and red nitridosilicate (Ba,Sr,Ca)₂Si₅N₈:Eu are highly suitable.

This phosphor system is on the one hand matched to the indium radiation because it has substantial components in both the UV and blue spectral ranges, both of which are absorbed equally well. This mixture is moreover also suitable for conventional fluorescent lamps. It may also be used in an indium lamp based on high pressure, as is known per se from U.S. Pat. No. 4,810,938. Green improvement is possible. The lamp has a conventional discharge vessel with a metal halide fill. The radiation strikes a phosphor layer on the outer bulb, which converts part of the primary radiation into green radiation components. The phosphor layer consists of Ba—SiON:Eu. This technique is described in principle for example in U.S. Pat. No. 6,958,575.

Further information is contained in Tabs 4a and 4b below. Tab. 4a relates to excitation with a wavelength of 400 nm. Tab. 4b relates to excitation with a wavelength of 460 nm. For various exemplary embodiments, the two tables shows the weigh-in stoichiometry, the concentration of the activator, the color locus components x and y, the dominant wavelength, the relative quantum efficiency Q.E. and the relative brightness in percent.

Another exemplary embodiment is an LED module consisting of at least one set of three light-emitting LEDs, red, green and blue. This RGB module is used for the excitation of LCD display screens or RPTV devices. The green LED is a primarily UV-emitting pc-LED (phosphor conversion LED), which is converted by means of a novel green Ba—SiON into green radiation. The peak wavelength of the UV LED is in particular 400 nm. The temperature rises slightly during operation of the module to 200° C., which the thermally stable phosphor copes with easily.

In principle, it is also possible to replace Si at least partially by Ge, preferably by up to 20 mol %. Full replacement is nevertheless also possible.

Instead of Ba and/or Sr alone, Ca and/or Mg and/or Zn and/or Cu may also be constituents of the cation M. The proportion is preferably not more than 30 mol % of the cation M.

Instead of only with Eu and/or Ce, the novel phosphor may also be codoped with Mn or Yb as well. Good results are provided in particular by Eu, Yb codoping. Furthermore, Tb³⁺ may also be used as an activator, alone or in combination with the others. While doping with Ce leads to a UV- to blue-emitting phosphor under UV excitation, particularly with the known Hg line 254 nm, the pure Tb variant emits green with the same UV excitation.

FIG. 14 shows the emission spectrum of a Tb³⁺-doped sample of the phosphor (Ba_(0.95)Tb_(0.05))₂Si₅O₉N₂ with excitation in the UV range at 254 nm. This Tb³⁺-doped sample shows a typical line emission, as is often observed in the case of Tb³⁺ emission. This phosphor may furthermore be sensitized with Ce, according to the formula Ba₂Si₅O₉N₂:(Tb,Ce). For this phosphor, the excitability tends to be at a longer wavelength and more resembles that of the pure Ce-doped sample.

FIG. 15 shows the emission spectrum of the Ce-doped sample

(Ba_(0.98)Ce_(0.02))₂Si₅O₉N₂ for excitation at 338 nm. This exemplary embodiment gives blue-violet illumination. FIG. 16 shows the excitation spectrum of the same sample, the emission having been observed at 378 nm.

Tab. 5 contrasts various doped phosphors of the Ba₂Si₅O₉N₂:D type with the doping D=Eu, D=Ce or D=Tb, as well as D=(Eu,Mn) and D=(Eu,Ce). The color locus components x and y are respectively specified. The Eu-doped exemplary embodiment is used as a reference. In comparison therewith, an (Ea,Ce)-codoped sample shows no shift of the color locus since the Ce band for excitation in the range of from 370 to 400 nm is not significant.

The Ce-doped sample gives blue-violet illumination. The Tb-doped sample is found to be a green line radiator. Incorporation of Mn²⁺ as codoping with Eu²⁺ is possible in small amounts. Ce-doped and Ce,Tb-codoped phosphors are also suitable for fluorescent lamps or other UV light sources such as excimer radiators, which excite in the far UV range and for example use triple-band mixing. By means of the novel Ce-doped and Ce,Tb-codoped SiON phosphors, it is therefore even possible to produce a light source for near UV or with peak emission at about 380 to 390 nm. In this case, the SiON is the only phosphor. The excitation, which is readily possible in the range of from 250 to 375 nm, is achieved particularly efficiently in the range of from 290 to 340 nm.

In general the efficiency, particularly of the Tb³⁺ and Ce³⁺-doped exemplary embodiments, can be optimized when incorporating therein small amounts of Li⁺ and/or Na⁺, which are used for charge compensation. Either the additional positive charge can generally be introduced by means of monovalent ions such as Li or Na, or alternatively a slight modification of the Ba/Si ratio or a slight modification of the O/N ratio may be carried out.

What is essential is the property of the new thermally stable phosphor, that it comes from the M-Si—O—N system having a cation M, M being represented by Ba or Sr alone or as a mixture or may additionally be combined with at least one other element from the group Ca, Mg, Zn, Cu, the phosphor being activated with Eu or Tb alone or as a mixture, optionally in codoping with Mn, the activator D partially replacing the cation M. Since the phosphor is produced from the charge stoichiometry MO—Si₃O₂—Si₃N₄ with an increased oxygen content relative to the known phosphor MSi₂O₂N₂, it preferably has essentially the composition aMO×bSiO₂×c Si₃N₄. Its stoichiometry therefore essentially follows the formula M_(a)Si_(b+3c)O_(a+2b)N_(4c).

Here, it is not necessary for a,b,c to be integers. The phosphor is furthermore distinguished in that the ratio O:M is >1 and in that the ratio O:Si is >2.

Particularly good results are shown by a phosphor in which the relations between a, b and c are kept so that: b:c=4.8 to 8.0 and/or a:c=3.5 to 5.5. Preferably, b:c lies in the range of from 5 to 6 and/or a:c lies in the range of from 3.5 to 4.

A phosphor which is particularly outstanding in this regard has the charge stoichiometry Ba₉Si₂₁O₃₆N₁₀, or expressed another way Ba₃Si₇O₁₂N_(3.3). This phosphor can be produced with particularly high phase purity by the production method indicated above, and shows excellent efficiency.

FIG. 17 shows a comparison of the powder brightness of a phosphor with the charge stoichiometry Ba₃Si₇O₁₂N_(3.3):D, a sample with D=10% Eu expressed in terms of the Ba component having been compared with a sample of the same type, but with the difference that here D=9.75% Eu+0.25% Yb was selected. FIG. 17 shows that the addition of Yb leads to an about 3% higher powder brightness, compared with pure Eu doping.

FIG. 18 shows a comparison of the powder brightness of an Eu-doped phosphor type with the charge stoichiometry Ba₃Si₇O₁₂N_(3.33), relative to the powder brightness of the phosphor type with the charge stoichiometry Ba₃Si₆O₁₂N₂. In this case, the production conditions were varied in the same way, which led to the specimens 1 to 7. Irrespective of the production conditions, the powder brightness of the phosphor with the charge stoichiometry Ba₃Si₇O₁₂N_(3.33) is always higher, and specifically between 2 and 28% higher than that of a phosphor which is based on a weigh-in according to the charge stoichiometry Ba₃Si₆O₁₂N₂. A radiographic structure analysis of these samples with the charge stoichiometry Ba₃Si₇O₁₂N_(3.33) leads to the result that these samples have the smallest linewidth (least average microdistortion) of all the samples studied. The indexing gives a trigonal or hexagonal space group with a=7.5094(1) Å and c=6.4753(1) Å with a cell volume V=316.23 Å³. The space groups P3 or P-3 give an unequivocal description of the barium positions taking into account the volume increments of possible composition. From the radiographic characterization, taking into account the electroneutrality, the phosphor shows an ideal composition Ba_(2.5)Si₆O_(11.5)N₂. If, however, an attempt is made to produce a phosphor with the composition Ba₃Si₆O₁₂N₂ by selecting Ba₃Si₆O₁₂N₂ as the charge stoichiometry, then essentially a phase with small lattice constants a and c and a significant component of the heterogeneous phase BaSi₂O₅ is obtained as an end product, cf. Tab. 3. In general, phosphors of the type with the stoichiometry M_(2.5)Si₆O_(11.5)N₂, where in particular M=Ba alone or predominantly at more than 50 mol %, show outstanding properties. In particular, the doping in this case is Eu or (Eu,Yb) or Ce.

FIG. 19 shows a comparison of the powder brightness as a function of the holding time at high temperature. The holding time during the anneal is indicated in hours. The temperature of 1300° C. in the anneal shows an optimal holding time in the range of about 5 to 8 hours. Good results are achieved in a time period of between 4 and 10 hours.

FIG. 20 shows the effect of the fluxing agent on the powder brightness. Fluxing agents achieve an increase in the powder brightness, which is about 2 to 30% depending on the fluxing agent. Particularly suitable are chlorides, above all of Ba and Sr, and carbonates, above all of Li. Preferred fluxing agent components in the charge stoichiometry are between 0.01 and 5 wt %, the value range of between 0.1 and 3 wt % being particularly suitable.

FIG. 21 represents a phase diagram similarly as in FIG. 3. The charge stoichiometries Ba₂Si_(4.6)O_(8.6)N_(1.8) and Ba₂Si₅O₉N₂ and Ba₃Si₇O₁₂N_(3.3), which show particularly high efficiency and the phase purity, are represented. They all lie in a band in which the SiN_(4/3) component lies between 20% and 30%. The charge stoichiometry preferably lies in the quadrilateral indicated, which also has the SiO₂ component limit lines of from 65 to 75%. On the other hand, the specimen Ba₃Si₆O₁₂N₂ is at an SiN_(4/3) component of about 17% and has much worse phase purity and efficiency. For the stoichiometry of the Ba₃Si₇O₁₂N_(3.3) charge, the ratio BaCO₃:SiO₂ is about 1:1.5. The SiN_(4/3) component is about 25%. The uncertainty relates to the Eu doping content, which is usually introduced by means of Eu₂O₃. A mass spectroscopy study of the annealed charge stoichiometry Ba₃Si₇O₁₂N_(3.3) (N:O=1:3.6) confirmed the increased nitrogen content relative to the stoichiometry Ba₃Si₆O₁₂N₂ (N:O=1:6). The compounds in FIG. 21 are to be understood as phosphors with 2% Eu for Ba, i.e. for example M=(Ba_(0.99)Eu_(0.02)) as the cation M in M₃Si₇O₁₂N_(3.3).

Tab. 6a represents characteristics of the structure for various phosphors with different charge stoichiometries, which predominantly lie in the SiN_(4/3) component range of from 20 to 30%. The doping content is 2 mol % Eu. The lattice constants a and c as well as the heterogeneous phase component are specified.

Tab. 6b shows, for various exemplary embodiments, the weigh-in stoichiometry, the efficiencies, the color locus components x and y, the dominant wavelength and the relative quantum efficiency Q.E. in percent, and specifically for an excitation wavelength of 400 nm. The doping content is 2 mol % Eu.

TABLE 6a Heterogeneous Charge phase Sample a (in Å) c (in Å) stoichiometry component (%) BP 376/07 7.514 6.479 Ba₃Si₇O₁₁N₄ 21% BaSi₂O₂N₂ <3% BaSi₂O₅ BP 377/07 7.510 6.478 Ba₃Si₇O₁₃N_(2.67) — BP 378/07 7.509 6.480 Ba₃Si₇O₁₄N₂ 29% BaSi₂O₅ BP 379/07 7.510 6.476 Ba₃Si₇O₁₂N_(3.33) — BP 380/07 7.513 6.482 Ba_(2.5)Si_(7.5)O_(12.5)N_(3.33) — BP 381/07 7.513 6.478 Ba_(2.5)Si_(7.5)O_(13.5)N_(2.67) <3% BaSi₂O₅ BP 382/07 7.512 6.481 Ba_(2.5)Si_(7.5)O_(11.5)N₄ —

TABLE 6b Sample BP Charge λ_(dom) Rel. Q.E. ---/07 stoichiometry x y (nm) (%) 174 Ba₃Si₆O₁₂N₂ 0.258 0.591 537 95 376 Ba₃Si₇O₁₁N₄ 0.250 0.616 536 58 377 Ba₃Si₇O₁₃N_(2.67) 0.252 0.630 538 98 378 Ba₃Si₇O₁₄N₂ — — — — 379 Ba₃Si₇O₁₂N_(3.33) 0.252 0.626 538 100 380 Ba_(2.5)Si_(7.5)O_(12.5)N_(3.33) 0.252 0.625 538 75 381 Ba_(2.5)Si_(7.5)O_(13.5)N_(2.67) — — — — 382 Ba_(2.5)Si_(7.5)O_(11.5)N₄ 0.250 0.623 537 78

TABLE 3 Sample BP---/ Weigh-in Phase composition Rel. Q.E. 07 stoichiometry according to XRD x y λ_(dom) (nm) (%) 121 Ba₄Si₅O₈N₂ — 0.259 0.623 539 61 122 Ba₁Si₅O_(4.4)N_(4.4) — 0.248 0.607 535 55 123 Ba_(1.3)Si₁O₃N_(0.2) — 0.167 0.555 510 84 124 Ba_(1.3)Si_(1.45)O_(3.2)N_(0.66) — 0.271 0.511 532 6 126 Ba₁Si₉O₃N_(10.7) New phase, Si₃N₄ — — — — 127 Ba₁Si₉O₅N_(9.3) New phase, Si₃N₄ 0.244 0.586 532 33 128 Ba₁Si₄O₂N_(4.65) Ba₂SiO₄, Si₃N₄ 0.170 0.517 507 31 129 Ba₁Si₉O₇N₈ New phase, Si₃N₄ 0.241 0.595 532 25 130 Ba₁Si₄O₃N₄ New phase, Si₃N₄ — — — — 131 Ba₁Si_(2.3)O_(1.67)N_(2.67) Ba₂SiO₄, Si₃N₄ — — — — 132 Ba₁Si₉O₉N_(6.7) New phase, Si₃N₄ 0.245 0.599 534 30 133 Ba₁Si₄O₄N_(3.35) New phase 0.253 0.612 537 66 134 Ba₁Si_(2.3)O_(2.3)N_(2.22) ? 0.182 0.505 507 16 135 Ba₁Si_(1.5)O_(1.5)N_(1.68) Ba₂SiO₄, Si₃N₄ — — — — 136 Ba₁Si₉O₁₁N_(5.3) New phase, Si₃N_(4,) 0.247 0.602 534 33 SiO₂ 137 Ba₁Si₄O₅N_(2.65) New phase 0.250 0.613 536 70 138 Ba₁Si_(2.3)O₃N_(1.77) ?, BaSiO₃ — — — — 139 Ba₂Si₃O₄N_(2.65) Ba₂SiO₄ — — — — 140 Ba₁Si₁O_(1.4)N_(1.06) Ba₂SiO₄ — — — — 141 Ba₁Si₉O₁₃N₄ ?, SiO₂ 0.254 0.590 535 30 142 Ba₁Si₄O₆N₂ New phase, BaSi₂O₅ 0.256 0.618 538 55 143 Ba₁Si_(2.3)O_(3.67)N_(1.33) New phase, ? 0.252 0.621 537 50 144 Ba₂Si₃O₅N₂ ?, BaSiO₃ — — — — 145 Ba₅Si₅O₉N₄ Ba₂SiO₄ — — — — 146 Ba₁Si_(0.67)O_(1.3)N_(0.67) Ba₂SiO₄ 0.174 0.545 510 63 147 Ba₁Si₉O₁₅N_(2.67) New phase, SiO₂ 0.255 0.602 537 58 148 Ba₂Si₈O₁₄N_(2.67) ? 0.264 0.623 540 67 149 Ba₁Si_(2.3)O_(4.3)N_(0.9) New phase 0.255 0.622 538 100 150 Ba₁Si_(1.5)O₃N_(0.668) BaSiO₃ — — — — 151 Ba₁Si₁O_(2.2)N_(0.534) Ba₂SiO₄, SiO₂ 0.167 0.545 510 70 152 Ba₁Si_(0.67)O_(1.67)N_(0.445) Ba₂SiO₄ — — — — 153 Ba₁Si_(0.43)O_(1.3)N_(0.38) Ba₂SiO₄ — — — — 154 Ba₁Si₉O₁₇N_(1.3) SiO₂, BaSi₂O₅ 0.274 0.586 541 39 155 Ba₁Si₄O₈N_(0.65) SiO₂, BaSi₂O₅ — — — — 156 Ba₁Si_(2.3)O₅N_(0.43) BaO (?), BaSi₂O₅ 0.262 0.616 540 92 157 Ba₂Si₃O₇N_(0.65) New phase, BaSi₂O₅ 0.282 0.567 542 42 158 Ba₁Si₁O_(2.6)N_(0.26) Ba₂SiO₄, SiO₂ 0.180 0.551 512 25 159 Ba₁Si_(0.67)O_(2.8)N_(0.216) Ba₂SiO₄ 0.163 0.547 509 108 160 Ba₁Si_(0.43)O_(1.57)N_(0.19) Ba₂SiO₄, Ba₃SiO₅ 0.410 0.501 569 86 161 Ba₁Si_(0.25)O_(1.25)N_(0.163) Ba₃SiO₅ 0.517 0.465 582 94 168 Ba₃Si₇O₁₄N₂ New phase, BaSi₂O₅ 0.260 0.621 539 95 169 Ba_(0.7)Si_(1.3)O_(2.7)N_(0.4) New phase, SiO₂ 0.260 0.585 537 77 170 Ba_(0.7)Si_(1.3)O_(2.5)N_(0.524) New phase SiO₂ 0.258 0.613 538 44 171 Ba₃Si₇O_(12.5)N_(3.3) New phase, BaSi₂O₅ 0.254 0.621 538 100 172 Ba₁Si₃O₅N_(1.33) New phase, BaSi₂O₅ 0.260 0.619 539 75 173 Ba₁Si₃O_(5.4)N_(1.068) New phase, BaSi₂O₅ 0.262 0.622 540 73 174 Ba₃Si₆O₁₂N₂ New phase, BaSi₂O₅ 0.258 0.591 537 100 175 Ba₂Si₅O₉N₂ New phase 0.255 0.623 536 100 415 Ba₃Si₇O_(12.5)N_(3.3) New phase 0.252 0.629 538 116 418 Ba₃Si₇O_(12.5)N_(3.3) New phase 0.252 0.629 538 113 416 Ba₃Si₆O₁₂N₂ New phase, BaSi₂O₅ 0.254 0.604 537 112 419 Ba₃Si₆O₁₂N₂ New phase, BaSi₂O₅ 0.252 0.593 536 107

TABLE 4a Sample Activator Rel. BP---/ Weigh-in conc. λ_(dom) Rel. Q.E. Brightness 07 stoichiometry (mol %) Exc (nm) x y (nm) (%) (%) 230 Ba₁Si_(2.3)O_(4.3)N_(0.9) 2 400 0.254 0.624 538 81 54 230 a Ba₁Si_(2.3)O_(4.3)N_(0.9) 2 400 0.254 0.630 538 84 76 231 Ba₃Si₆O₁₂N₂ 2 400 0.253 0.583 534 80 53 231 a Ba₃Si₆O₁₂N₂ 2 400 0.250 0.592 534 81 63 232 Ba₂Si₅O₉N₂ 2 400 0.255 0.625 538 81 56 232 a Ba₂Si₅O₉N₂ 2 400 0.252 0.630 538 81 76 415 Ba₃Si₇O₁₂N_(3.3) 2 400 0.252 0.629 538 97 61 233 Ba₂Si₅O₉N₂ 4 400 0.268 0.629 542 86 74 233 a Ba₂Si₅O₉N₂ 4 400 0.265 0.634 541 80 89 236 Ba₂Si₅O₉N₂ 5 400 0.269 0.632 542 79 79 237 Ba₂Si₅O₉N₂ 10 400 0.296 0.632 548 63 75 240 Ba₃Si₆O₁₂N₂ 5 400 0.269 0.602 541 81 72 241 Ba₃Si₆O₁₂N₂ 10 400 0.296 0.619 548 65 76 244 Ba₁Si_(2.3)O_(4.3)N_(0.9) 5 400 0.269 0.634 542 86 86 245 Ba₁Si_(2.3)O_(4.3)N_(0.9) 10 400 0.296 0.633 548 69 85 498 Ba₃Si₇O₁₂N_(3.3) 5 400 0.272 0.633 543 100 82 499 Ba₃Si₇O₁₂N_(3.3) 10 400 0.302 0.629 549 92 100

TABLE 4b Sample Activator Rel. BP---/ Weigh-in conc. λ_(dom) Rel. Q.E. Brightness 07 stoichiometry (mol %) Exc (nm) x y (nm) (%) (%) 230 Ba₁Si_(2.3)O_(4.3)N_(0.9) 2 460 0.259 0.630 540 78 37 230 a Ba₁Si_(2.3)O_(4.3)N_(0.9) 2 460 0.259 0.636 540 86 63 231 Ba₃Si₆O₁₂N₂ 2 460 0.256 0.628 539 81 34 231 a Ba₃Si₆O₁₂N₂ 2 460 0.257 0.633 539 86 45 232 Ba₂Si₅O₉N₂ 2 460 0.260 0.629 540 75 39 232 a Ba₂Si₅O₉N₂ 2 460 0.256 0.363 539 81 63 233 Ba₂Si₅O₉N₂ 4 460 0.273 0.633 543 85 58 233 a Ba₂Si₅O₉N₂ 4 460 0.269 0.639 543 85 87 236 Ba₂Si₅O₉N₂ 5 460 0.274 0.636 544 84 74 237 Ba₂Si₅O₉N₂ 10 460 0.300 0.633 549 69 86 240 Ba₃Si₆O₁₂N₂ 5 460 0.273 0.634 543 96 62 241 Ba₃Si₆O₁₂N₂ 10 460 0.300 0.633 549 88 94 244 Ba₁Si_(2.3)O_(4.3)N_(0.9) 5 460 0.274 0.638 544 91 81 245 Ba₁Si_(2.3)O_(4.3)N_(0.9) 10 460 0.301 0.635 549 78 100 498 Ba₃Si₇O₁₂N_(3.3) 5 460 0.272 0.633 543 100 75 499 Ba₃Si₇O₁₂N_(3.3) 10 460 0.302 0.629 549 96 94

TABLE 5 λ_(Exc) Sample Number Charge stoichiometry (nm) x y BP 234/07 (Ba_(0.99)Eu_(0.01))₂Si₅O₉N₂ 400 0.25 0.62 BP 319/07 (Ba_(0.98)Eu_(0.01)Ce_(0.01))₂Si₅O₉N₂ 400 0.25 0.62 BP 319/07 (Ba_(0.98)Eu_(0.01)Ce_(0.01))₂Si₅O₉N₂ 370 0.25 0.62 BP 320/07 (Ba_(0.98)Eu_(0.02))₂Si₅O₉N₂ 370 0.18 0.15 BP 320/07 (Ba_(0.98)Eu_(0.02))₂Si₅O₉N₂ 338 0.18 0.12 BP 320/07 (Ba_(0.98)Eu_(0.02))₂Si₅O₉N₂ 290 0.18 0.12 BP 322/07 (Ba_(0.95)Tb_(0.05))₂Si₅O₉N₂ 254 0.21 0.61 BP 323/07 Ba_(0.98)Eu_(0.01)Mn_(0.01))₂Si₅O₉N₂ 400 0.25 0.62 BP 323/07 Ba_(0.98)Eu_(0.01)Mn_(0.01))₂Si₅O₉N₂ 370 0.25 0.62 

1. A thermally stable phosphor made of the M-Si—O—N system, having a cation M and an activator D, M being represented by Ba or Sr alone or as a mixture and optionally also being combined with at least one other element from the group Ca, Mg, Zn, Cu, the phosphor being activated with Eu or Ce or Tb alone or as a mixture, optionally in codoping with Mn or Yb, the activator D partially replacing the cation M, wherein the phosphor is produced from the charge stoichiometry MO—SiO₂—SiN_(4/3) with an increased oxygen content relative to the known phosphor MSi₂O₂N₂:D, where MO is an oxidic compound.
 2. The phosphor as claimed in claim 1, wherein the component MO was introduced by means of a compound MCO₃.
 3. The phosphor as claimed in claim 1, wherein M=Ba alone or predominantly, i.e. more than 50%.
 4. The phosphor as claimed in claim 2, wherein the MCO₃:SiO₂ ratio of the charge mixture is between 1:1.5 and 1:2, including the endpoint values.
 5. The phosphor as claimed in claim 4, wherein the SiN_(4/3) component of the charge mixture in the system MCO₃—SiO₂—SiN_(4/3) is at least 15%.
 6. The phosphor as claimed in claim 5, wherein the SiN_(4/3) component is at least 20%.
 7. The phosphor as claimed in claim 1, wherein the phosphor itself has the stoichiometry M_(2.5)Si₆O_(11.5)N₂, where M=Ba alone or predominantly at more than 50 mol %.
 8. The phosphor as claimed in claim 1, wherein the phosphor essentially has the stoichiometry M_(a)Si_(b+3c)O_(a+2b)N_(4c), where b:c=4.8 to 8.0 and/or a:c=3.5 to 5.5.
 9. The phosphor as claimed in claim 8, wherein b:c lies in the range of from 5 to 6 and at the same time a:c lies in the range of from 3.5 to
 4. 10. A light source having a phosphor as claimed in claim
 1. 11. The light source as claimed in claim 10, wherein the light source is an LED.
 12. A method for producing a phosphor as claimed in claim 1, wherein the method comprises: a) homogenizing the substances MCO₃, SiO₂, Si₃N₄ and the precursor of the activation substance, in particular an oxide of D, preferably Eu₂O₃ alone or in combination with Yb oxide, for several hours, in particular from 2 to 6 hours; b) mixing the substances while maintaining a MCO₃:SiO₂ ratio of between 1:1.5 and 1:2, including the endpoint values; c) first annealing of the charge mixture under reducing conditions, at a temperature of from 1200 to 1400° C., for several hours, in particular for from 4 to 10 hours; d) optionally grinding the anneal cake; e) optionally second annealing under reducing conditions, at a temperature of from 850° C. to 1450° C.
 13. The method as claimed in claim 12, wherein the component MO was introduced by means of a compound MCO₃.
 14. The method as claimed in claim 13, wherein the MCO₃:SiO₂ ratio of the charge mixture is between 1:1.5 and 1:2, including the endpoint values.
 15. The method as claimed in claim 14, wherein the SiN_(4/3) component of the charge mixture in the preparation of the system MCO₃—SiO₂—SiN_(4/3) is at least 15%.
 16. The method as claimed in claim 15, wherein the SiN_(4/3) component is at most 30%.
 17. The method as claimed in claim 11, wherein a fluxing agent is used with a proportion of at most 5 wt % expressed in terms of the charge stoichiometry without a fluxing agent.
 18. The phosphor as claimed in claim 5, wherein the SiN_(4/3) component of the charge mixture in the system MCO₃—SiO₂—SiN_(4/3) is at most 55%.
 19. The phosphor as claimed in claim 6, wherein the SiN_(4/3) component is at most 30%.
 20. The method as claimed in claim 15, wherein the SiN_(4/3) component of the charge mixture in the preparation of the system MCO₃—SiO₂—SiN_(4/3) is at most 55%.
 21. The method as claimed in claim 17, wherein the fluxing agent is a chloride or carbonate. 